US10174242B1 - Coated thioaluminate phosphor particles - Google Patents
Coated thioaluminate phosphor particles Download PDFInfo
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- US10174242B1 US10174242B1 US15/993,116 US201815993116A US10174242B1 US 10174242 B1 US10174242 B1 US 10174242B1 US 201815993116 A US201815993116 A US 201815993116A US 10174242 B1 US10174242 B1 US 10174242B1
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000002245 particle Substances 0.000 title claims abstract description 35
- 150000004767 nitrides Chemical class 0.000 claims abstract description 28
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 239000010410 layer Substances 0.000 claims description 21
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 20
- 239000011247 coating layer Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- 229910002601 GaN Inorganic materials 0.000 claims description 12
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052693 Europium Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical group [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000001429 visible spectrum Methods 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 2
- 229910052788 barium Inorganic materials 0.000 claims 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims 2
- 239000011777 magnesium Substances 0.000 claims 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 2
- 238000000576 coating method Methods 0.000 abstract description 70
- 239000011248 coating agent Substances 0.000 abstract description 57
- 238000000034 method Methods 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 230000004888 barrier function Effects 0.000 abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 36
- 238000012360 testing method Methods 0.000 description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 23
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000000231 atomic layer deposition Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000012190 activator Substances 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000008393 encapsulating agent Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- 229910052984 zinc sulfide Inorganic materials 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000005243 fluidization Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000005083 Zinc sulfide Substances 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- FZBINJZWWDBGGB-UHFFFAOYSA-L strontium 3,4,5-trihydroxythiobenzate Chemical compound [Sr++].Oc1cc(cc(O)c1O)C([O-])=S.Oc1cc(cc(O)c1O)C([O-])=S FZBINJZWWDBGGB-UHFFFAOYSA-L 0.000 description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 229910052946 acanthite Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- -1 rare earth activated sulfide Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- XXUJMEYKYHETBZ-UHFFFAOYSA-N ethyl 4-nitrophenyl ethylphosphonate Chemical compound CCOP(=O)(CC)OC1=CC=C([N+]([O-])=O)C=C1 XXUJMEYKYHETBZ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/44—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the coatings, e.g. passivation layer or anti-reflective coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
Definitions
- the invention relates generally to coated thioaluminate phosphor particles and to methods for coating thioaluminate phosphor particles.
- LED lighting has delivered huge improvements in energy efficient lighting while simultaneously enabling high quality.
- Another feature of LED lighting is the very long life of the lighting product, typically with an L70 (the amount of time a light source will operate before its lumen output drops to 70% of its initial output) greater than 25,000 hours.
- the incumbent light sources LEDs replace typically have L70 of 10,000 hours (fluorescent lighting) or catastrophic failure at about 1000 hours (incandescent).
- This long life is a function of all components in the LED light source, but especially the blue or violet emitting diode and the down-converting phosphor materials which absorb light emitted by the diode and convert it to other colors to complete the visible spectrum.
- the diode degrades, the LED becomes less bright, but retains its color balance.
- a phosphor degrades the LED typically becomes less bright and also loses its color balance.
- the LED may take on a non-white hue. Color shift is typically more problematic from the user perspective.
- the most common architecture for LED packages is to disperse a phosphor material in a silicone matrix to form a slurry and deposit this slurry into a reflective cup area which also includes the light emitting diode.
- the package has two types of reflective areas, a diffuse reflective surface typically made of plastic or ceramic and a more specular reflective surface which is formed from the electrical contacts.
- the specular reflective surfaces are plated with silver to significantly enhance the reflectivity and increase light extraction from the package.
- An LED phosphor is usually made up of an activator ion, typically divalent europium or trivalent cerium, in a host.
- the activator ion directly absorbs the incoming light and emits light of a longer wavelength in a process typically called down-conversion. That is, an incident photon is down-converted from a higher energy blue photon to a lower energy photon, such as cyan, green, yellow, orange, or red.
- the host helps tune the absorptive and emissive wavelengths of the activator. Additionally, the degree of crystallinity of the host around the activator can play a large role in the efficiency of absorption and emission.
- Phosphor degradation is typically attributed to the action of water or oxygen in the presence of the heat and light produced by the LED. It has become common practice to coat many types of phosphors with a layer to prevent the water or oxygen from coming in contact with the phosphor and facilitating degradation. Typically, these coatings are inorganic oxides, and are deposited on the phosphor either by a solution phase, e.g. sol-gel, reaction, or a vapor phase reaction.
- a phosphor can typically degrade through three mechanisms.
- oxidation of the activator can eliminate its 4f orbital to 5d orbital charge transfer absorption, rendering it unable to absorb the incident light.
- the host may deform chemically, changing the energy of the activator's absorption and emission.
- the host may deform physically, losing crystallinity around the activator, and decreasing the efficiency of the activator's absorption and emission.
- a low temperature chemical change to the host will also result in a loss of crystallinity.
- the overall impact of these degradations is dependent upon the extent to which the host, in either its pristine or degraded state, allows the water or oxygen to permeate through the material. For example, degradation of cerium doped yttrium aluminum garnet phosphor materials is very slow relative to europium doped alkali earth orthosilicate phosphors.
- sulfide-based phosphors e.g., thioaluminate phosphors
- a hydrolysis reaction with water can release sulfur from the phosphor which can degrade performance by, for example, tarnishing the reflective surfaces in the LED package. This blackening can vastly decrease the light output of the phosphor-converted LED.
- failure to properly coat sulfide phosphors can create a larger problem than failure to properly coat oxide or nitride phosphors.
- thioaluminate phosphor particles have a coating comprising, consisting essentially of, or consisting of a nitride.
- the nitride coating may comprise, consist essentially of, or consist of aluminum nitride, gallium nitride, or a mixture thereof, for example.
- the nitride coatings on the thioaluminate phosphor particles provide a significantly improved barrier to water, compared to an aluminum oxide coating. This improvement may be due to non-reactivity of the nitride coating precursor with the volatilized gases from an unstable sulfide phosphor surface.
- a phosphor converted LED comprises such nitride coated thioaluminate phosphor particles.
- FIG. 1 shows a schematic of an example fluidized bed reactor for chemical vapor deposition on phosphor particles.
- FIG. 2 shows x-ray photoelectron spectroscopy spectra in the sulfur 2p region for two coated phosphor samples.
- FIG. 3 shows example thermal gravimetric—mass spectroscopy data for a sample of an uncoated calcium thioaluminate phosphor.
- FIG. 4A shows a microscope image of a sample of ZnS coated with Al 2 O 3 after an AgNO 3 test.
- FIG. 4B shows a microscope image of a sample of ZnS coated with AlN after an AgNO 3 test.
- FIG. 4C shows a microscope image of calcium thioaluminate phosphor particles coated with Al 2 O 3 after an AgNO 3 test.
- FIG. 4D shows a microscope image of calcium thioaluminate phosphor particles coated with AlN after an AgNO 3 test.
- Sulfide phosphors can have very attractive spectral properties. Specifically, the emission spectrum of many sulfide phosphors can be very narrow, characterized by a full width at half maximum (FWHM) of less than 50 nm, and sometimes as little 25 to 30 nm. This spectral narrowness can be extremely attractive in display backlighting and general lighting applications.
- FWHM full width at half maximum
- Divalent rare earth activated sulfide phosphors of interest include RE 1-w A w M x E y , where RE may be one or more rare earth elements (for example, Eu or Gd), A may be one or more elements selected from the group Mg, Ca, Sr, or Ba, M may be one or more elements selected from the group Al, Ga, B, In, Sc, Lu or Y, E comprises sulfur and optionally at least one of Selenium, Oxygen, and Tellurium, w is greater than or equal to zero, and less than or equal to about 0.99 or less than or equal to 1.0, 2 ⁇ x ⁇ 4, and 4 ⁇ y ⁇ 7.
- RE may be one or more rare earth elements (for example, Eu or Gd)
- A may be one or more elements selected from the group Mg, Ca, Sr, or Ba
- M may be one or more elements selected from the group Al, Ga, B, In, Sc, Lu or Y
- E comprises sulfur and optionally at least one of Selenium, Oxygen, and Tell
- Such phosphors may be referred to herein as thioaluminate or calcium thioaluminate phosphors. Typically, they are capable of absorbing blue or ultraviolet light and in response emitting light having a peak wavelength in the green region of the visible spectrum.
- thioaluminate phosphors may react with water to release H 2 S and convert part of the sulfide host to oxide. This change impacts the optical properties of the phosphor, typically shifting the absorption to much higher energy as well as decreasing the absorption and emission intensities due to a decrease of crystallinity around the activator center.
- Free sulfide such as that which can be released from hydrolysis of sulfide phosphors as H 2 S or similar species, can disrupt the packaging on several levels. At high concentrations, it can inhibit the curing of silicones used for encapsulation. This inhibition of curing means that phosphor can move within the package, shifting the color point of the LED, and that the wire bonds from the contacts to the die are not protected, making the LED more prone to catastrophic failure from breakage of the electrical connections. At lower concentrations, the sulfide can react over time to corrode and blacken the silver of the electrical contact pads and the gold of the wire bond from the contact to the die. This latter degradation mechanism can also come into play if cationic sulfur sources, such as SO 2 , are present, and may be accelerated by the electrochemical potential present as current flows through the package.
- cationic sulfur sources such as SO 2
- coating phosphor particles can inhibit the progress of water into the phosphor and impede its degradation.
- Common methods of coating are the creation of a silica layer by a sol-gel process or an alumina layer by chemical vapor deposition.
- the phosphor particles are suspended in a solvent.
- the solvent contains a coating precursor, and a reaction is initiated to form the precursor into a continuous coating on the phosphor particles.
- the precursor may be initiated in the presence of the phosphor, or it may be initiated prior to introduction of the phosphor.
- phosphor may be stirred in an aqueous or ethanolic solution of tetraethoxysilane (TEOS).
- TEOS tetraethoxysilane
- the coating process may then be initiated by the addition of an ammonia solution to change the pH and accelerate the rate of hydrolysis of the silane forming a silica coating on the phosphor.
- Other types of precursors are known, such as ethanolic titanium isopropoxide and aqueous aluminum nitrate. Many other sol-gel chemistries are known and may be utilized.
- a chemical vapor deposition process is typically performed on particles which have been fluidized in a fluidized bed.
- Creation of the fluidized bed typically entails placing the phosphor powder in a column that has a gas permeable but powder impermeable membrane or frit at the bottom. The powder is suspended by the upward force of the gas which counteracts the downward force of gravity. This fluidization enables access to all surfaces of the phosphor particles which might not otherwise be exposed in solid powder or even in a stirred solution.
- a second gas stream may carry a second precursor for the coating, and may deliver it to near the middle of the fluidization zone.
- An example fluidized particle coating system is depicted in FIG. 1 .
- One such fluidization system arrangement uses argon as a fluidizing gas, and in two separate streams bubbles the argon through water then up through the frit and through trimethyl aluminum (TMA) then into the midst of the fluidization zone. These reactants are mixed in the fluidization zone, and the zone is heated to 100° C.-300° C. The hydrolysis of TMA then proceeds to form an amorphous aluminum oxide coating on the phosphor particles.
- TMA trimethyl aluminum
- Other inert carrier gases can be used besides argon, for example nitrogen.
- An alumina coating may also be deposited in a layer by layer process, sometimes called atomic layer deposition (ALD), where the phosphor particles are treated with a small concentration of water to form a water/hydroxide layer on the surface of the particles, the reaction chamber is evacuated to remove all the water and then filled with a small concentration of TMA, which reacts with the surface hydroxyls left from the water to form an aluminum oxide layer. The chamber is again evacuated to and filled with a low concentration of water, and the steps are repeated until the desired number of layers have been deposited.
- ALD atomic layer deposition
- the exact thickness of the coating will be determined, in part, by the method used; ALD will form the thinnest coating layer, CVD will form a thicker coating, while sol-gel will generally form a much thicker coating.
- a phosphor is tested as part of packaged LEDs by observing its lumen maintenance and color shift over a period of time under different conditions.
- a typical test would be a high temperature operating life (HTOL) test, where the LEDs are powered on in a test oven at an elevated temperature. Typical temperatures for HTOL testing are 85° C. and 125° C., and typical durations are 1008 hours and 6000 hours.
- Another typical test would be a wet, high temperature operating life (WHTOL) test, where the LEDs may be powered on the entire time, or may be power cycled at regular intervals in a test oven at an elevated temperature and elevated, controlled humidity.
- WHTOL wet, high temperature operating life
- Typical conditions for WHTOL testing are 60° C./90% relative humidity (60/90) and 85° C./85% relative humidity (85/85), and the typical duration is 1008 hours.
- Success criterion may vary depending on who is administering the test, but generally lumen maintenance should be at least greater than 80% after 1008 hours of WHTOL testing. That is, the brightness at the end should be at least 80% of the initial brightness, and color shift as measured by ⁇ u′v′ (the change in color coordinates as measured in CIE 1976 color space from the beginning of the test period to the end of the test period) should be at least less than 0.007.
- coated sulfide phosphors may be tested for the effectiveness of the coating in sealing in the sulfur by subjecting the phosphor powder to a solution of silver nitrate.
- the silver ions in solution will react with any sulfide that has not been shielded from the solution by the coating and form black Ag 2 S. This black precipitate is readily visible once formed, and the time to its appearance can be used as a gauge of the effectiveness of the coating.
- the inventors then developed an improved coating method that involves coating the thioaluminate phosphor material with a nitride layer rather than with aluminum oxide.
- Aluminum nitride, gallium nitride, and mixtures of the two may be suitable for such coatings, for example.
- pure ammonia, or ammonia with an inert gas is used as the fluidizing gas and trimethyl aluminum can be used as the aluminum source to deposit an aluminum nitride layer.
- trimethyl gallium may be substituted for the trimethyl aluminum to deposit a gallium nitride layer instead of an aluminum nitride layer.
- a mixed aluminum nitride and gallium nitride layer may be deposited by using both trimethyl aluminum and trimethyl gallium in the process.
- Another coating layer such as for example alumina, silica, or alumina and silica may optionally be added above the aluminum nitride layer, by for example one of the coating methods described above.
- alumina, silica, or alumina and silica may optionally be added above the aluminum nitride layer, by for example one of the coating methods described above.
- oxide or other layers above and below the nitride layer.
- Table 1 below presents data for a series of coating runs, all of which were run with the same phosphor lot. These data are, for each coating experiment, a reference number, the amount of phosphor charged to the reactor, the amount of phosphor recovered, the temperature that the reactor was held at during the coating cycle, the duration of the coating cycle, the flow rate of the argon gas through the trimethyl aluminum bubbler and into the reactor (L/min), the flow rate of anhydrous ammonia into the reactor (L/min), the weight ratio of nitrogen and aluminum precursor used, and the theoretical amount of aluminum nitride formed in relation to the amount of phosphor in the reactor.
- Table 2 below presents spectroscopic data on the phosphor sample before coating, and after each of the coating runs. Additionally, a separate lot of phosphor was coated by ALD and spectroscopic data is presented for the sample prior to coating and after coating.
- Thioaluminate samples coated with aluminum nitride or with Al 2 O 3 were tested by subjecting the phosphor powder to the silver nitrate solution test described above. In these tests, several mg of coated phosphor were placed in a small vial. A few mL of 0.01 M AgNO 3 (aq) were added to the vial, and the time recorded when a predetermined level of blackening due to the formation of silver sulfide was observed by the naked eye. The recorded time is the time to failure (TTF), and gives a relative gauge of the effectiveness of the coating. Table 3 below reports AgNO 3 time to failure for a sample with the best Al 2 O 3 coatings, a sample with an AlN coating deposited by ALD, and two samples with CVD AlN coatings.
- TTF time to failure
- samples were attached to glass slides with double-sided tape, immersed in silver nitrate solution, and observed over the course of several hours.
- Four samples were compared: zinc sulfide coated with Al 2 O 3 , shown in FIG. 4A ; zinc sulfide coated with AlN, shown in FIG. 4B ; a thioaluminate phosphor sample, NBG20180301, coated with a previously identified best alumina coating, shown in FIG. 4C ; and a sample of the same phosphor lot coated with AlN (example NBG20180327), shown in FIG. 4D . After about 8 hours the samples were compared.
- the zinc sulfide with alumina coating showed no darkening, while the zinc sulfide with aluminum nitride coated showed some percentage of darkening.
- the phosphor sample with alumina coating had a few green phosphor particles left, however it had almost entirely darkened ( FIG. 4C ), while the aluminum nitride coated sample appeared less than half darkened ( FIG. 4D ).
- the nitride coated thioaluminate phosphors of the present invention may be optically coupled with an excitation source in any conventional manner.
- One of the more common methods is to combine green emitting phosphors, such as the nitride coated thioaluminate phosphors disclosed here, with a red phosphor and optional blue and/or yellow phosphors.
- the phosphors may be combined together and then added to an encapsulant, such as silicone, epoxy, or some other polymer, or the phosphors may be combined during their addition to the encapsulant.
- the phosphor loaded encapsulant may then be placed in the optical path of an excitation source, such as an LED or laser diode that emits ultraviolet, violet, or blue light.
- One common method is to deposit the slurry of phosphor or phosphors into an LED (light emitting diode) package which contains an LED die. The slurry is then cured forming an encapsulated LED package.
- Other methods include forming the encapsulant into a shape or coating the encapsulant onto a substrate which may already be in a particular shape, or may be subsequently formed into a particular shape.
- the phosphor containing encapsulant may be disposed on or near (e.g., coated on) the in-coupling region of a light guide, or on the out-coupling region of a light guide, such as a light guide intended for use in a display.
- the phosphor composition may be deposited as a thin film on the LED die or on another substrate and subsequently optically coupled to the light source.
- the combination of an excitation source and the phosphors of the present invention may be used in general lighting, niche lighting applications, display backlighting, or other lighting applications.
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Abstract
Description
TABLE 1 |
Coating run data |
% | ||||||||
Coating | Mass, | Mass, | Reactor | Reactor | Rate, | Rate, | NH3/TMA | AlN |
Sample # | Initial | Final | Temp. | time | Ar/TMA | NH3 | wt ratio | eq |
NBG20180326 | 1 | 0.5 | 300 | 1 | 0.030 | 0.029 | 9.9 | 7.3% |
NBG20180327 | 1.2 | 0.7 | 300 | 1 | 0.016 | 0.013 | 9 | 3.1% |
NBG20180328 | 1.1 | 0.66 | 250 | 1 | 0.012 | 0.011 | 9.3 | 2.7% |
NBG20180329 | 1.5 | 0.9 | 300 | 1.5 | 0.016 | 0.011 | 7.3 | 3.7% |
TABLE 2 |
Spectroscopic data: |
Coating Sample # | λpeak (nm) | FWHM (nm) | PL % |
Uncoated | 528 | 40 | 107 |
NBG20180326 | 527 | 41 | 83 |
NBG20180327 | 527 | 41 | 94 |
NBG20180328 | 526 | 41 | 94 |
NBG20180329 | 526 | 41 | 90 |
Uncoated | 527 | 39 | 113 |
AlN by |
525 | 40 | 69 |
nm | |||
TABLE 3 |
AgNO3 resistance test data: |
AgNO3 TTF, | ||
Coating Sample # | hours | |
(a) Al2O3 | 0.3 | |
(b) AlN by ALD | 0.5 | |
(c) AlN by CVD | 3 | |
(NBG20180326) | ||
(d) AlN by CVD | 4.5 | |
(NBG20180327) | ||
Claims (20)
0≤w≤1.0;
2≤x≤4; and
4≤y≤7;
0≤w≤1.0;
2≤x≤4; and
4≤y≤7;
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US15/993,116 US10174242B1 (en) | 2018-05-17 | 2018-05-30 | Coated thioaluminate phosphor particles |
MX2020012365A MX2020012365A (en) | 2018-05-17 | 2019-05-15 | Coated thioaluminate phosphor particles. |
CA3100380A CA3100380A1 (en) | 2018-05-17 | 2019-05-15 | Coated thioaluminate phosphor particles |
CN201980048101.7A CN112437801A (en) | 2018-05-17 | 2019-05-15 | Coated thioaluminate phosphor particles |
JP2020564402A JP7447023B2 (en) | 2018-05-17 | 2019-05-15 | Coated thioaluminate phosphor particles, light-emitting device containing luminescent composition, and method for producing coated thioaluminate phosphor particles |
KR1020207036448A KR20210011969A (en) | 2018-05-17 | 2019-05-15 | Coated Thioaluminate Phosphor Particles |
PCT/US2019/032466 WO2019222384A1 (en) | 2018-05-17 | 2019-05-15 | Coated thioaluminate phosphor particles |
EP19802997.7A EP3794091A4 (en) | 2018-05-17 | 2019-05-15 | Coated thioaluminate phosphor particles |
TW108117086A TWI837130B (en) | 2018-05-17 | 2019-05-17 | Coated thioaluminate phosphor particles |
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